JPS59157112A - Manufacture of urethane acrylate oligomer - Google Patents

Abstract

PURPOSE:To obtain photocurable titled oligomer capable of providing flexible coating film, by the reaction between a specific hydroxyl group-contg. isocyanurate, a reaction product from a hydroxyl group-contg. acrylate and diisocyanate, etc., with one or more components epsilon-caprolacton-modified. CONSTITUTION:The objective oligomer can be obtained by the reaction between (A) tris(2-hydroxyethyl)isocyanurate and/or an epsilon-caprolacton-modified polyol derived therefrom and (B) an ethylenic unsaturated monoisocyanate prepared by the reaction between a hydroxyalkyl(meth)acrylate and/or its epsilon-caprolacton- modified derivative and organic diisocyanate with either or both components containing epsilon-caprolacton-modified product(s).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides modified e-caprolactone having a tris(2-hydroxyethyl)in cyanurate skeleton. Relating to lettane acrylate oligomers. More specifically, the present invention relates to a photocurable urethane acrylate oligomer that provides a cured coating film with excellent flexibility.

The photocurable oligomer obtained in the present invention is a flexible vinyl
It is expected to be applied to floor tiles, optical fibers, plastic coatings, etc.

One of the recent successes in the trend towards low-pollution, resource-saving, and energy-saving paints is UV-curable paints. It consists of a reactive composition containing a reactive diluent which reacts during curing to become part of the protective coating itself, containing a substantially volatile agent. Tris (2-
Some are based on urethane acrylates having a skeleton of hydroxyethyl)in cyanurate. However, since this urethane acrylate-based composition has a very high viscosity, it is necessary to reduce the viscosity by diluting it with a low boiling point acrylic reactive diluent that is highly irritating to the skin of dog fish. Application to the substrate had to be carried out. Furthermore, the photocured cured coating film of this urethane acrylate-based composition was electrically hard (brittle and inflexible).

Therefore, the present inventors conducted intensive research to improve the drawbacks of paint compositions based on urethane acrylates having such a tris(2-hydroxyethyl)in cyanurate skeleton. caprolactone-modified tris(2-hydroxyethyl)isocyanurate obtained by ring-opening 6-caprolactone and hydroxyalkyl (meth)acrylate or &ma-8-caprolactone-modified hydroxyalkyl (meth)acrylate and An original curable urethane acrylate oligo marker obtained by a urethanization reaction with an ethylenically unsaturated monoisocyanate obtained by the reaction of an organic diisocyanate, has a lower viscosity than a caprolactone-unmodified one, and has a cured coating film. discovered that the elongation and tensile strength were improved and completed the present invention.

That is, the present invention is (A))! Js(2-hydroxyethyl)isocyanurate and/or 6-cub+77chton modified tris(2
-hydroxyethyl) isocyanurate (hereinafter referred to as polyol) and (B) hydroxyalkyl (meth)acrylate and/or C-caprodictone-modified hydroxyalkyl (meth)acrylate (hereinafter referred to as acrylic compound having a hydroxyl group) ) and an ethylenically unsaturated monoisocyanate obtained from the reaction with an organic diisocyanate, in a combination in which a small amount of the above (A) and (B) (one of which contains an ε-caprolactone modified product) is used. A method for producing a urethane acrylate oligomer, characterized by:

The reaction according to the invention is typically carried out as follows. First step,
Hydroxyalkyl (meth)acrylate and/or ε
- A carblocton-modified hydroxyalkyl (meth)acrylate is reacted with an organic diisocyanate to produce an ethylenically unsaturated monoisocyanate. This ethylenically unsaturated monoisocyanate is then reacted with the polyol to yield the desired product.

The polyol (A) used in the present invention is tris(2-hydroxyethyl)in cyanurate and/or ε-capro2
It is tris(2-hydroxyethyl) isocyanurate modified with methane, and ring-opening addition polymerization of 0.1 to 10 mole parts of e-caprolactone to 1 mole part of tris(2-hydroxyethyl) isocyanurate. 120 with a polyester compound terminated with a human dioxyl group.
Those having a hydroxyl value in the range of ~645 Da KOH/l/ are preferred.

The ring-opening polymerization of ζ-kag02 chtone to water [G] of tris(2-hydroxyethyl)in cyanurate is carried out at 100-240'C, preferably 120-200'C under N2 atmosphere.
Perform at a temperature of It is preferable to use a catalyst for this reaction. As a catalyst, titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, tetraethyl titanate, tin octylate, dibutyl tin oxide,
As the organic tin compound such as dibutyltin dilaurate, stannous chloride, stannous bromide, stannous iodide, etc. can be used. Use, jiha 0.1 for total preparation iK
ppm 1000 ppm.

The product of such a reaction is actually of formula (I) aH2aH,o
A mixture of compounds represented by -fo(aH2)5oH1 (where m, , m2.m3 are each 0 or a positive number, and the average of m2 + J is 0.1 to 1o) It is statistically distributed from the reaction product to the polycarrolactone compound.

It should be noted that there is no need to further separate or purify this reaction product, and it can be used as it is in the next step of the reaction.

Tatlis (
2-Hydroxyethyl) incyanurate is a viscous liquid that is fluid at room temperature, and serves as a source of excellent reactivity in the next step and the production of highly flexible final products.

In addition, in the present invention, the reaction between the Acrif compound having a hydroxyl group and the organic diisocyanate is carried out at a charging molar ratio (former/
The latter) is carried out in a reaction temperature range of about 171° C. to 90° C., preferably 40° to 60° C., and is itself a conventional reaction.

The acrylic compound having a hydroxyl group used in the present invention is a hydroxyalkyl (meth)acrylate and/or a 6-caprodicone variable hydroxyalkyl (meth)acrylate. .2 to 20 mole parts 6
- Cap02 chtone is preferably ring-opening addition polymerized.

Examples of the hydroxyalkyl (meth)acrylate used in the present invention include 2-human xyethyl acrylate or methacrylate, hydroxypentyl acrylate or methacrylate, and hydroxypentyl acrylate or methacrylate. Hydroxyethyl (meth)acrylate is particularly effective.

The ε-turnip ratio to the hydroxyl group of hydroxyalkyl (meth)acrylate was 70 to 1 in a sudden atmosphere.
It is carried out at a temperature of 50°C, preferably 80-140°C. 7
This is because if it is lower than 0°C, the reaction rate is low, and if it is higher than 150°C, the acrylate group or methacrylate group will undergo radical polymerization. It is preferable to use a catalyst for this reaction. Examples of catalysts include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate, organic tin compounds such as tin octylate, dibutyltin oxide, and dibutyltin dilaurate, and stannous chloride, beautified stannous, and stannous iodide. Tin etc. can be used. The amount used is 0.1 ppm to 1.0 ppm for the entire preparation lid. OD D ppm.

In addition, during the reaction, hydroquinone, quinone monomethyl ether, p-t
-7'tilcatechol, 7-functional nothiazine, etc. from 0.02 to
It is preferable to add 2%.

The product of such a reaction actually has the formula (i) 1 (wherein R1 is hydrogen or a methyl group, R2 has 2 to 6 carbon atoms)
alkylene group, n is 0 or a positive number, and the average of n is 0.
2 to 20), which are statistically distributed from unreacted substances to polycaprolactone compounds. It should be noted that there is no need to further separate and load this reaction product, and it can be used as is for the next step of the reaction.

The hydroxyalkyl (meth)acrylate modified with σ-kaguro 2 chton used here is a liquid with fluidity at room temperature, has excellent reactivity in the next step, and is the source of the final product with rich circularity. Become.

Examples of the organic diisocyanate used in the present invention include commercially available tolylene diisocyanate mixtures, hexamethylene diisocyanate, diphenylmethane-4,4-diisocyanate, xylene diisocyanate, and isophore diisocyanate. Among these, isofonate diisocyanate is particularly preferred because it has good weather resistance and because one isocyanate group is much more reactive than the other, it is easy to synthesize an ethylenically unsaturated monoisocyanate.

The urethanization reaction between an organic diisocyanate and an acrylic compound having a hydroxyl group can be carried out using any known urethanization catalyst such as amines, tin compounds, or metal acetylacetonate complexes. The catalysts include triethylenediamine, morpholine, N-ethylmorpholine, piperidine, tritanolamine, triethylene diamine, dibutyltin dilaurate, stannous octaate, stannous X-y chlorate, stannous oleate,
Examples include i-th tin dolate, digityltin oxide, and the like.

In the present invention, the reaction between the ethylenically unsaturated monoisocyanate and the polyol is carried out at a charging molar ratio (former/latter) of about 371 and a temperature range of 60 to 90°C, and is itself a conventional reaction.

Further, at this time, a catalyst may or may not be used.

When the photocurable oligomer of the present invention is used as a photocurable coating agent, it may be used together with a liquid ethylenically unsaturated phase compound that acts as a diluent to further lower the viscosity.

The liquid ethylenically unsaturated compounds t and ``c'' include, for example, 2-hydroxyethyl acrylate, phenoxyethyl acrylate, inbornyl acrylate, styrene, vinylpyrrolidone, and nato-2hydrofurfuryl acrylate.These diluents include oligomers. fm m
It is desirable to use 10 to 60% of fK. Particularly preferably 20 to 40%. Polyfunctional diluents such as trimethylolpropane triacrylate may be present to maintain the unique combination of strength and elongation of this invention by maintaining the distance between the shade bonding sites. , it is preferred to use a monoethylenic diluent.

Even if a photosensitizer is used appropriately in the coating agent (,
Ketonic photosensitizers such as benzophenone and jetoxyacetophenone and benzoin ether-based sensitizers such as benzoin butyl ether and benzoin methyl ether can be used.

If the intended final product is manufactured using the original curable oligomer according to the present invention, it is possible to improve flexibility and form a cured layer with excellent VFI layer properties and abrasion resistance. It can be widely used as an excellent material in the fields of flexible vinyl floor tiles, optical fiber coatings, and plastic coatings.

The tris(2-hydroxyethyl)ine cyanurate-based original curable oligomer of the present invention will be explained below with reference to examples, but the present invention is not limited to these.

Manaka-gun means the foothills of Mu.

Example 1 (B1) Air introduction pipe, temperature range [, cooling pipe, and stirring device it fa: 1ift.
ε-caprolactone 1.140 parts (10.0 mol), 2
-Hydroxyethyl acrylate1. l5Ofil(1
0.0 mol), hydroquinone monomethyl ether 11
．． 5 groups and 0.115 parts of stannous chloride were added, and while introducing air, the reaction was carried out at 120°C for about 10 hours to obtain ε-
The reaction stopped when caprolactone Asami was below 1%.

2.500 parts of ε-caprolactone-modified 2-hydroxyethyl acrylate was obtained as a reaction product. The hydroxyl value of this acrylic compound was 2449-KOH/&.

(B2) In addition, 2.20 parts (1 o, o mol) of isophoro/diisocyanate and 2.20 parts (1 o, o mol) of isophoro/diisocyanate and dibutyltin diisocyanate were placed in a 5-shade 5-glass flask equipped with an air introduction tube, a temperature control tube, a cooling tube, a dropping funnel, and a stirring device. lauray) was added and kept at 60°C in an air atmosphere. Furthermore, the reaction temperature (
ε-caprolactone-modified 2-hydroxyethyl acrylate synthesized in (B1) while maintaining the temperature (below 60°C)
2,500 parts (1 o, o mol) was dropped from the dropping funnel over about 2 hours, and after the dropping was completed, the reaction was continued at 60°C for about 5 hours, and the reaction product was confirmed to have no hydroxyl group by IR analysis. After confirming this, the reaction was stopped. 4.520 parts of liquid ethylenically unsaturated monoisocyanate was obtained as a reaction product.

(0) 1 Then, in a 5-tube flask similar to (B2), add 522
(2.0 mol) and 5Ω0 parts of methyl ethyl ketone were charged and heated to 80°C. Furthermore, 2.712 parts (6
, 0 mol] was added dropwise from the dropping funnel over about 4 hours while maintaining the reaction temperature (below 80°C) in an air atmosphere, and after the completion of the dropping, the reaction was carried out at 80°C for about 5 hours, so that N00% was 0.01
The reaction stopped at the end. Subsequently, methyl ethyl ketone was expelled under reduced pressure to obtain 3,234 parts of original curable oligomer.

The viscosity of this oligomer at 25°C is 11.000 cps
Met.

′! Example A 2 Into a 5-e4 flask equipped with a thermometer, a cooling tube, and a stirring device, 1277 parts (11.2 moles) of C-caprolactone and tris(2-hydroxy Add 2925 parts (11.2 mol) of ethyl isocyanurate and 4.2 parts of nat-2-butyl titanate, and react at 170°C under a wood-lined atmosphere for about 6 hours, stopping the reaction when I-caprolactone remains 1 it 1% or less. did. 4,200 parts of ε-caprolactone-modified tris(2-hydroxyethyl)incyanuride was obtained as a reaction product. The hydroxyl value of this polyol is 449 In9-KOH/!
/Met.

(0) Next, in the same manner as CG of Example 1, (A
) 750 parts (2.0 mol) of δ-capro2-modified tris(2-hydroxyethyl)in cyanurate synthesized in (B2) of Example 1 were mixed with 2712 parts of ethylenically unsaturated phase monoisocyanate synthesized in (B2) of Example 1. (6.0 mol) to obtain a one-component curable oligomer -5462H'!-.The viscosity of this oligomer at 25°C was 65,000 cps.
Met.

Comparative Example 1 (B) In the same manner as in (B2) of Example 1, 1,160 f& of 2-hydroxyethyl acrylate was reacted with 2,220 parts of isophorone diisocyanate (diptyltin dilaurate as a catalyst). 6.76 parts used) 3680 parts of ethylenically unsaturated phase monoisocyanate were obtained.

(C) Next, in the same manner as in Example 1 (0), 522 parts of tris(2-hydroxyethyl) isocyanurate was reacted with the ethylenically unsaturated phase monoisocyanate 2o28tJ synthesized in the above (B) to form the original curable oligomer 255
I got 0 copies. The viscosity of this oligomer at 25°C is 200
．． It was more than D00ops.

Application Examples Comparative Examples - * Using the photocurable oligomers shown in Table 1 produced in the same manner as the flow side and those, a diluent and a photosensitizer were combined, and a cured coating film was obtained by UV irradiation. . The results are shown in Table 1.

In the test, the blending ratio of oligomer/diluent/photosensitizer (Irgacure 651, Ciba Geigy product name) was 75%.
/25/1.9C storm weight ratio) was applied to glass. Curing was performed by irradiating the coated sample using a high pressure mercury lamp rung of 80 W/cm.

The film thickness was approximately 100μ.

Pour THKiO: ) Lis(2-and droxyethyl)in cyanurate g-CL: g-caprolactone HICA: 2-hydroxyethyl acrylate tpDi: Isoborone diisocyanate f12)
POEA: Phenoxyethyl acrylate THFA
: Tetrahydrone rufuryl acrylate N-VP: N-vinylpyrrolidone TiCGDA : ) jj Ethylene glycol diacrylate Note 5) Test method is based on JIS-K-6501, applicant's agent Kaoru Furuya

Claims (1)

[Scope of Claims] 1(^tris(2-hydroxyethyl)isocyanurate and/or 6-caprolactone modified tris(2-
(B) hydroxyalkyl (meth)acrylate and/or 6-caprolactone-modified hydroxyalkyl (meth)acrylate (hereinafter referred to as an acrylic compound having a hydroxyl group); Ethylenic diisocyanate obtained from reaction with organic diisocyanate! Method 2 for producing urethane acrylate oligomers, characterized by reacting phase I monoisocyanate with a combination of a small amount of the above (A) and (B) (both of which contain a 6-caprodictone modified product). The polyol is tris (2- and droxyethyl)
5. Method for producing a urethane acrylate oligomer according to claim 1, which is a reaction product obtained by polymerizing 1% (parts K) of t-caprolactone (isocyanurate) and 0.1 to 10 moles of t-caprolactone. An acrylic compound having a hydroxyl group is added to 1 mole part of hydroxyalkyl (meth)acrylate, and ε-capro2
A method for producing a urethane acrylate oligomer according to Claim 1g4 or 2, which is a reaction product obtained by polymerizing 0.2 to 20 mol parts of a ) The acrylate is 2-hydroxyethyl acrylate or methacrylate, hydroxyethyl acrylate or methacrylate, hydroxypentyl acrylate or methacrylate, Claim 1, 2 or 3K
Method for producing urethane acrylate oligomers on sr25. The organic diisocyanate is a tolylene diisocyanate mixture, hexamethylene diisocyanate,
A method for producing a urethane acrylate oligomer according to any one of claims 1 to 4, which is diphenylmethane-4,4'-diisocyanate, xylene diisocyanate, or inphorone diisocyanate.